EP0144033B1 - Substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-one - Google Patents

Substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-one Download PDF

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EP0144033B1
EP0144033B1 EP84113928A EP84113928A EP0144033B1 EP 0144033 B1 EP0144033 B1 EP 0144033B1 EP 84113928 A EP84113928 A EP 84113928A EP 84113928 A EP84113928 A EP 84113928A EP 0144033 B1 EP0144033 B1 EP 0144033B1
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carbon atoms
formula
chlorine
cycloalkyl
fluorine
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EP0144033A3 (en
EP0144033A2 (en
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Heinz Dr. Ziemann
Karl-Heinrich Dr. Mohrmann
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/16—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/16—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C07C49/163—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/16—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C07C49/167—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/213—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C49/217—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C07C49/223—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C07C49/23—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C07C49/233—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings
    • C07C49/235—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to new substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-one, a process for their preparation and their use as intermediates for the synthesis of substances with plant growth-regulating and fungicidal activity.
  • ketones to be used as starting materials for carrying out the process according to the invention are generally defined by the formulas (IIa), (IIb) and (IIc).
  • R ' stands for cycloalkyl with 5 to 7 carbon atoms, cycloalkenyl with 5 to 7 carbon atoms and phenyl which is optionally monosubstituted to trisubstituted, identically or differently, by alkyl having 1 to 3 carbon atoms.
  • R 2 represents phenyl which is optionally monosubstituted to trisubstituted identically or differently by alkyl having 1 to 3 carbon atoms.
  • ketones of the formula (Ila), (llb) and (llc) are not yet known.
  • ketones of the formula (IIa) can be prepared by butan-2-one of the formula (III) in which X and Y have the meanings given above, with aldehydes of the formula (IV) in which R 'has the meanings given above, in the presence of a diluent, such as an alcohol, and in the presence of a base, such as an alkali metal hydroxide or carbonate, at temperatures between 10 ° C and 80 ° C.
  • a diluent such as an alcohol
  • a base such as an alkali metal hydroxide or carbonate
  • butan-2-ones of the formula (III) and the aldehydes of the formula (IV) are known compounds of organic chemistry.
  • acetylene derivatives of the formula (V) and the pivalic acid halides of the formula (VI) are known compounds of organic chemistry.
  • ketones of the formula (IIc) can be prepared by ketones of the formulas or in which R 2 , X and Y have the meanings given above, with hydrogen in the presence of a diluent, such as methanol, and in the presence of a catalyst, such as Raney nickel or palladium on carbon, under normal pressure or under elevated pressure, such as preferably 30 to 40 bar, at temperatures between 20 ° C. and 40 ° C. selectively hydrogenated on the double bond or triple bond.
  • a diluent such as methanol
  • a catalyst such as Raney nickel or palladium on carbon
  • the process according to the invention is carried out in the liquid phase, preferably in the presence of diluents, using a suspended, powdery hydrogenation catalyst.
  • the hydrogenation according to the invention can be carried out batchwise or continuously as bottom or trickle-phase hydrogenation in known hydrogenation reactors, such as autoclaves, autoclave cascades, tubular reactors or circulation reactors.
  • the preferred procedure is the discontinuous bottom phase hydrogenation in an autoclave at elevated pressure.
  • Inert organic solvents are suitable as diluents when carrying out the process according to the invention.
  • These preferably include alcohols, such as methanol, ethanol, isopropanol or ethylene glycol; Ethers such as diethyl ether, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, dioxane or tetrahydrofuran; saturated hydrocarbons such as n-heptane or cyclohexane; as well as esters, such as ethyl acetate.
  • alcohols such as methanol, ethanol, isopropanol or ethylene glycol
  • Ethers such as diethyl ether, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, dioxane or tetrahydrofuran
  • saturated hydrocarbons such as n-heptane or cyclohexane
  • esters
  • Hydrogenation catalysts suitable for the process according to the invention are, for example, those which consist of metals and / or compounds of elements of the eighth subgroup of the periodic system of the elements according to Mendeleev or which contain them.
  • the metals ruthenium, rhodium, palladium, platinum, cobalt and nickel and their compounds are preferred.
  • the metal compounds can be, for example, oxides, hydroxides and / or oxyhydrates.
  • the metals can be copper. Vanadium, molybdenum. Chromium and / or manganese and compounds of these metals are present.
  • the hydrogenation catalysts can consist exclusively or predominantly of hydrogen-transferring substances, but these can also be applied to support materials.
  • Possible carrier materials for the hydrogen-transferring substances are, for example: inorganic materials, such as kieselguhr, silica, aluminum oxide, alkali and alkaline earth silicates, aluminum silicates, montmorillonite, zeolites, spinels, dolomite, kaolin, magnesium silicates, zirconium oxide, zinc oxide, calcium carbonate, Silicon carbide, aluminum phosphate, boron phosphate, asbestos, activated carbon or barium sulfate, but also organic materials, for example naturally occurring or synthetic compounds with high molecular weights such as silk, polyamides, polystyrenes, cellulose or polyurethanes. Inorganic carrier materials in powder form are preferred.
  • Such supported catalysts can generally contain 0.5 to 50% by weight, preferably 1 to 10% by weight, of the hydrogen-transferring substance, based on the total mass of the supported catalyst.
  • the hydrogen-transferring substance can be distributed homogeneously in the support material, but catalysts are preferred, in whose outer layer or on the surface of which the hydrogen-transferring substance is deposited.
  • the preparation and shaping of the catalysts which can be used in the process according to the invention can be carried out in a known manner (see, for example, Houben-Weyl, Methods of Organic Chemistry, Volume IV, Ic, Part I, pp. 16 to 26, Georg Thieme Verlag , Stuttgart, 1980).
  • Preferred supported catalysts are ruthenium on carbon, ruthenium on aluminum oxide, rhodium on carbon, rhodium on aluminum oxide, palladium on carbon, palladium on aluminum oxide, palladium on calcium carbonate, palladium on barium sulfate, palladium on silica, platinum on carbon and platinum on aluminum oxide, nickel on diatomaceous earth , Nickel on aluminum oxide and nickel and palladium on aluminum oxide.
  • Preferred hydrogenation catalysts which consist exclusively or predominantly of hydrogen-transferring substances are, for example, oxidic catalysts, such as palladium oxide, platinum oxide, ruthenium oxide and / or rhodium oxide / platinum oxide according to Nishimura, furthermore by reduction of corresponding metal salts or metal salt mixtures with alkali metal hydrides, alkali boronates, metal alkyls, hydrazine , Formaldehyde, hydrogen or electropositive metals black catalysts, such as palladium / black, platinum / black and rhodium / black; as well as skeletal catalysts of the Raney type, such as Raney nickel, Raney cobalt, Raney nickel cobalt, Raney nickel iron, Raney nickel copper. Raney nickel iron chromium, Raney nickel palladium and Raney nickel iron vanadium.
  • oxidic catalysts such as palladium oxide, platinum oxide, ruthenium oxide and / or rhodium oxide / platinum oxide according to Nis
  • ketones of the formulas (IIa) and (IIb) contain, as substituent R ', optionally substituted cycloalkenyl radicals or optionally substituted cycloalkyl radicals, those catalysts which contain or consist of nickel and / or palladium are those which are converted into saturated ketones of the formula (I) , particularly preferred.
  • ketones of the formulas (Ila) and (Ilb) contain substituted or unsubstituted aryl radicals as substituents R 'or if it is a ketone of the formula (IIc), those catalysts which are converted to saturated ketones of the formula (I) are ruthenium , Rhodium and / or platinum contain or consist thereof, particularly preferred.
  • the hydrogenation catalysts are used in the process according to the invention in such an amount that 0.05 to 2.5, preferably 0.1 to 1% by weight of hydrogen-transferring substance, based on the total weight of the reaction mixture, is present.
  • the catalytic activity of the hydrogenation catalysts is generally largely retained when the process according to the invention is carried out, so that they can be used repeatedly in a batch mode and can be used for a long time in a continuous mode.
  • reaction temperatures can be varied within a wide range. Generally one works in the range between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C.
  • reaction temperatures in the range from 20 ° C. to 60 ° C. are particularly preferred, while for the hydrogenation of aryl radicals
  • temperatures in the range from 60 ° C. to 120 ° C. are particularly preferred.
  • the hydrogenations according to the invention are preferably carried out at elevated pressure.
  • pressures in the range from 5 to 50 bar are particularly preferred, while for the hydrogenation of aryl radicals in the ketones of the formulas (IIa), (IIb) and (IIc) with the preferred catalysts, pressures in the range from 5 to 120 bar are particularly preferred.
  • the reaction time required for the process according to the invention depends on the reaction temperature, the hydrogen partial pressure, the intensity of the mixing of the reaction mixture and on the activity and concentration of the hydrogenation catalyst. In general, the reaction time required ranges from 15 minutes to several hours.
  • the simplest embodiment of the process according to the invention can be carried out discontinuously in the following manner:
  • a temperature-controlled autoclave provided with a stirring or mixing device is suitably treated with a ketone of the formula (Ila), (Ilb) or (IIc), the hydrogenation catalyst and charged with the diluent.
  • the mixture is heated to the selected reaction temperature with thorough mixing.
  • the course of the reaction can easily be followed by measuring the hydrogen consumption, which is compensated for by further hydrogen supply.
  • the hydrogenation is complete when no more hydrogen is consumed and the amount of hydrogen consumed corresponds approximately to the amount of hydrogen theoretically required.
  • reaction mixture is cooled, let down and worked up in a known manner, for example by filtering off the catalyst and distilling off the diluent.
  • the procedure is such that in a first stage ketones of the formula (IIa) which bear an optionally substituted aryl radical as substituents R 'are hydrogenated to corresponding ketones of the formula (IIc), which are then in a second stage Stage to the end products of formula (I) are hydrogenated (see also the preparation examples). It should be emphasized that only the C-C multiple bonds are hydrogenated with high selectivity, while the CO double bond is retained.
  • the new 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula (I) represent interesting intermediates for the synthesis of 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and -ols with fungicidal and plant growth regulating properties.
  • the 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and ols of the formula (VII) have strong fungicidal and plant growth-regulating properties (cf. EP-B 0 031 911 and EP-B 0 032 200).
  • the mixture used was pressurized with hydrogen up to a pressure of 30 bar and heated to 30 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was increased to 40 bar and maintained in accordance with the hydrogen consumption during the entire reaction time.
  • the product solution separated from the catalyst by filtration was reacted directly in the second stage without isolation.
  • the 2,2-bisfluoromethyl-5-phenyl-pentan-3-one obtained has a content of 98% (determined by gas chromatography).
  • the mixture used was pressurized with hydrogen up to a pressure of 50 bar and heated to 90 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was increased to 100 bar and maintained in accordance with the hydrogen consumption during the entire reaction time.
  • the product solution separated from the catalyst by filtration was freed of the methanol in a rotary evaporator.
  • the mixture was cooled to room temperature and depressurized to normal pressure.
  • the product solution separated from the catalyst by filtration was freed of methanol in a rotary evaporator.
  • the mixture used was pressurized with hydrogen up to a pressure of 30 bar and heated to 30 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was increased to 50 bar and maintained in accordance with the hydrogen consumption during the entire reaction time.
  • the product solution separated from the catalyst by filtration was freed of the methanol in a rotary evaporator.
  • the implementation takes place in accordance with the 2nd stage in process variant 1.
  • the mixture used was pressurized with hydrogen up to a pressure of 50 bar and heated to 50 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was increased to 70 bar and maintained in accordance with the hydrogen consumption during the entire reaction time.
  • the product solution separated from the catalyst by filtration was freed from the methanol on a rotary evaporator.
  • the mixture obtained was extracted twice with 1 liter of methylene chloride, the combined organic phases were washed four times with 2 liters of water, dried over sodium sulfate and the solvent was stripped off.
  • the present oily product was taken up in acetone and 326 g of naphthalene-1,5-disulfonic acid was added to the solution.
  • the precipitate that formed was suction filtered and suspended in 2 liters of methylene chloride. This suspension was shaken twice with 2 liters of saturated, aqueous sodium hydrogen carbonate solution. Then the organic phase was washed with 2 liters of water and, after drying over sodium sulfate, concentrated under reduced pressure.

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Description

Die vorliegende Erfindung betrifft neue substituierte 5-Cycloalkyl-2,2-dimethyl-pentan-3-one, ein Verfahren zu deren Herstellung und ihre Verwendung als Zwischenprodukte zur Synthese von Stoffen mit pflanzenwachstumsregulierender und fungizider Wirksamkeit.The present invention relates to new substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-one, a process for their preparation and their use as intermediates for the synthesis of substances with plant growth-regulating and fungicidal activity.

Es ist bereits bekannt geworden, daß sich Azolyl-methylketone als Zwischenprodukte zur Herstellung von Azolyl-Derivaten mit pflanzenwuchsregulierenden und fungiziden Eigenschaften verwenden lassen (vgl. EP-B 0 032 200 und EP-B 0031 911). So kann z. B. durch Umsetzung von 1-(1.2,4-Triazol-1-yl)-3,3- bis-fluormethyl-butan-2-on mit Cyclohexyl-methyl-bromid das 1-Cyclohexyl-2-(1,2,4-triazol-1-yl)-4,4-bis- fluormethyl-pentan-3-on nach folgendem Schema synthetisiert werden :

Figure imgb0001
It has already become known that azolyl methyl ketones can be used as intermediates for the preparation of azolyl derivatives with plant growth-regulating and fungicidal properties (cf. EP-B 0 032 200 and EP-B 0031 911). So z. B. by reacting 1- (1,2,4-triazol-1-yl) -3,3- bis-fluoromethyl-butan-2-one with cyclohexyl-methyl-bromide, 1-cyclohexyl-2- (1,2, 4-triazol-1-yl) -4,4-bis-fluoromethyl-pentan-3-one can be synthesized according to the following scheme:
Figure imgb0001

Nachteilig ist jedoch, daß bei dieser Art der Herstellung von Azolyl-Derivaten mit pflanzenwachstumsregulierender und fungizider Wirksamkeit die als Zwischenprodukte benötigten Azolyl-methyl-ketone nur durch mehrstufige Synthesen erhältlich sind und die dabei als Ausgangsstoffe eingesetzten Materialien zum Teil nur schwierig zugänglich sind.However, it is disadvantageous that in this type of production of azolyl derivatives with plant growth-regulating and fungicidal activity, the azolyl-methyl-ketones required as intermediates can only be obtained by multi-stage syntheses and the materials used as starting materials are sometimes difficult to access.

Es wurden nun neue substituierte 5-Cycloalkyl-2,2-dimethyl-pentan-3-one der Formel (I)

Figure imgb0002
in welcher

  • R für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Alkyl mit 1 bis 3 Kohlenstoffatomen substituiertes Cycloalkyl mit 5 bis 7 Kohlenstoffatomen steht,
  • X für Fluor oder Chlor steht und
  • Y für Wasserstoff, Fluor oder Chlor steht,

gefunden.New substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula (I)
Figure imgb0002
 in which
  • R represents cycloalkyl having 5 to 7 carbon atoms which is optionally monosubstituted to trisubstituted, identically or differently, by alkyl having 1 to 3 carbon atoms,
  • X represents fluorine or chlorine and
  • Y represents hydrogen, fluorine or chlorine,

found.

Weiterhin wurde gefunden, daß man die neuen substituierten 5-Cycloalkyl-2,2-dimethyl-pentan-3-one der Formel (I) erhält, wenn man Ketone der Formeln (IIa, Ilb oder IIc),

Figure imgb0003
Figure imgb0004
oder
Figure imgb0005
 in welchen

  • X und Y die oben angegebenen Bedeutungen haben,
  • Rl für jeweils gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Alkyl mit 1 bis 3 Kohlenstoffatomen substituiertes Cycloalkyl mit 5 bis 7 Kohlenstoffatomen, Cycloalkenyl mit 5 bis 7 Kohlenstoffatomen oder Phenyl steht und
  • R2 für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Alkyl mit 1 bis 3 Kohlenstoffatomen substituiertes Phenyl steht,

selektiv mit Wasserstoff in Gegenwart eines Hydrierkatalysators sowie gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.It was also found that the new substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula (I) can be obtained if ketones of the formulas (IIa, IIb or IIc),
Figure imgb0003
Figure imgb0004
 or
Figure imgb0005
 in which
  • X and Y have the meanings given above,
  • R 1 represents in each case optionally to triple, identical or different, cycloalkyl having 5 to 7 carbon atoms substituted by alkyl having 1 to 3 carbon atoms, cycloalkenyl having 5 to 7 carbon atoms or phenyl and
  • R 2 represents phenyl which is optionally monosubstituted to trisubstituted, identically or differently, by alkyl having 1 to 3 carbon atoms,

selectively with hydrogen in the presence of a hydrogenation catalyst and optionally in the presence of a diluent.

Schließlich wurde gefunden, daß die neuen substituierten 5-Cycloalkyl-2,2-dimethyl-pentan-3-one der Formel (I) sehr gut geeignet sind als Zwischenprodukte zur Herstellung von 4-Azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-onen und -olen mit pflanzenwachstumsregulierender und fungizider Wirksamkeit.Finally, it was found that the new substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula (I) are very suitable as intermediates for the preparation of 4-azolyl-5-cycloalkyl-2,2-dimethyl -pentan-3-ones and -ols with plant growth-regulating and fungicidal activity.

Überraschenderweise lassen sich pflanzenwachstumsregulierend und fungizid wirksame 4-Azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-one und -ole ausgehend von den erfindungsgemäßen substituierten 5-Cycloalkyl-2,2-dimethylpentan-3-onen der Formel (I) einfacher und in höherer Ausbeute herstellen als nach dem bisher bekannten Verfahren, bei dem die entsprechenden 4-Azolyl-2.2-dimethyl-butan-3-one als Zwischenprodukte eingesetzt wurden.Surprisingly, plant growth-regulating and fungicidally active 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and ols can be started from the substituted 5-cycloalkyl-2,2-dimethylpentan-3-ones of the formula ( I) easier and in higher yield than by the previously known process in which the corresponding 4-azolyl-2,2-dimethyl-butan-3-ones were used as intermediates.

Die erfindungsgemäßen Stoffe sind durch die Formel (I) allgemein definiert.The substances according to the invention are generally defined by the formula (I).

Bevorzugt sind Verbindungen der Formel (I) in denen

  • R für gegebenenfalls durch Methyl substituiertes Cyclohexyl steht;
  • X für Fluor steht und
  • Y für Wasserstoff oder Fluor steht.
Compounds of the formula (I) in which are preferred
  • R represents cyclohexyl optionally substituted by methyl;
  • X stands for fluorine and
  • Y represents hydrogen or fluorine.

Verwendet man beispielsweise 2,2-Bisfluormethyl-5-phenyl-pent-4-en-3-on und Wasserstoff als Ausgangsstoffe sowie Palladium und Ruthenium auf Aktivkohle als Katalysatoren, so kann der Reaktionsablauf des erfindungsgemäßen Verfahrens durch das folgende Formelschema wiedergegeben werden :

Figure imgb0006
If, for example, 2,2-bisfluoromethyl-5-phenyl-pent-4-en-3-one and hydrogen are used as starting materials and palladium and ruthenium on activated carbon as catalysts, the course of the reaction of the process according to the invention can be represented by the following formula:
Figure imgb0006

Verwendet man beispielsweise 2,2-Bisfluormethyl-5-(cyclohexen-1-yl)-pent-4-in-3-on und Wasserstoff als Ausgangsstoffe sowie Raney-Nickel als Katalysator, so kann der Reaktionsablauf des erfindungsgemäßen Verfahrens durch das folgende Formelschema wiedergegeben werden :

Figure imgb0007
If, for example, 2,2-bisfluoromethyl-5- (cyclohexen-1-yl) -pent-4-in-3-one and hydrogen as starting materials and Raney nickel as catalyst are used, the course of the reaction of the process according to the invention can be illustrated by the following formula are reproduced:
Figure imgb0007

Verwendet man beispielsweise 2,2-Bisfluormethyl-5-phenyl-pentan-5-on und Wasserstoff als Ausgangsstoffe und Ruthenium auf Aktivkohle als Katalysator, so kann der Reaktionsablauf des erfindungsgemäßen Verfahrens durch das folgende Formelschema wiedergegeben werden :

Figure imgb0008
If, for example, 2,2-bisfluoromethyl-5-phenyl-pentan-5-one and hydrogen are used as starting materials and ruthenium on activated carbon as a catalyst, the course of the reaction of the process according to the invention can be represented by the following formula:
Figure imgb0008

Die für die Durchführung des erfindungsgemäßen Verfahrens als Ausgangsstoffe zu verwendenden Ketone sind durch die Formeln (IIa), (Ilb) und (llc) allgemein definiert. In diesen Formeln steht R' für jeweils gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Alkyl mit 1 bis 3 Kohlenstoffatomen substituiertes Cycloalkyl mit 5 bis 7 Kohlenstoffatomen, Cycloalkenyl mit 5 bis 7 Kohlenstoffatomen und Phenyl. R2 steht für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Alkyl mit 1 bis 3 Kohlenstoffatomen substituiertes Phenyl.The ketones to be used as starting materials for carrying out the process according to the invention are generally defined by the formulas (IIa), (IIb) and (IIc). In these formulas, R 'stands for cycloalkyl with 5 to 7 carbon atoms, cycloalkenyl with 5 to 7 carbon atoms and phenyl which is optionally monosubstituted to trisubstituted, identically or differently, by alkyl having 1 to 3 carbon atoms. R 2 represents phenyl which is optionally monosubstituted to trisubstituted identically or differently by alkyl having 1 to 3 carbon atoms.

Die Ketone der Formel (Ila), (llb) und (llc) sind noch nicht bekannt.The ketones of the formula (Ila), (llb) and (llc) are not yet known.

Die Ketone der Formel (IIa) lassen sich herstellen, indem man Butan-2-one der Formel (III)

Figure imgb0009
in welcher X und Y die oben angegebenen Bedeutungen haben, mit Aldehyden der Formel (IV)
Figure imgb0010
in welcher R' die oben angegebenen Bedeutungen hat, in Gegenwart eines Verdünnungsmittels, wie beispielsweise eines Alkoholes, und in Gegenwart einer Base, wie beispielsweise eines Alkalihydroxides oder -carbonates, bei Temperaturen zwischen 10 °C und 80 °C umsetzt.The ketones of the formula (IIa) can be prepared by butan-2-one of the formula (III)
Figure imgb0009
 in which X and Y have the meanings given above, with aldehydes of the formula (IV)
Figure imgb0010
 in which R 'has the meanings given above, in the presence of a diluent, such as an alcohol, and in the presence of a base, such as an alkali metal hydroxide or carbonate, at temperatures between 10 ° C and 80 ° C.

Die Butan-2-one der Formel (III) und die Aldehyde der Formel (IV) sind bekannte Verbindungen der organischen Chemie.The butan-2-ones of the formula (III) and the aldehydes of the formula (IV) are known compounds of organic chemistry.

Die Ketone der Formel (Ilb) lassen sich herstellen, indem man Acetylen-Derivate der Formel (V)

Figure imgb0011
in welcher R1 die oben angegebenen bedeutungen hat, mit Pivalinsäurehalogeniden der Formel (VI),
Figure imgb0012
in welcher

  • X und Y die oben angegebenen Bedeutungen haben und .
  • Hal für Halogen, vorzugsweise Chlor oder Brom, steht,
in Gegenwart von Cu-(I)-Ionen als Katalysator und in Gegenwart eines Verdünnungsmittels, wie beispielsweise Toluol oder Pyridin, sowie in Gegenwart einer Base, wie beispielsweise Triethylamin, bei Temperaturen zwischen 20 °C und 100°C umsetzt.The ketones of the formula (IIb) can be prepared by using acetylene derivatives of the formula (V)
Figure imgb0011
 in which R 1 has the meanings given above, with pivalic acid halides of the formula (VI),
Figure imgb0012
 in which
  • X and Y have the meanings given above and.
  • Hal represents halogen, preferably chlorine or bromine,
in the presence of Cu (I) ions as a catalyst and in the presence of a diluent such as toluene or pyridine and in the presence of a base such as triethylamine at temperatures between 20 ° C and 100 ° C.

Die Acetylen-Derivate der Formel (V) und die Pivalinsäurehalogenide der Formel (VI) sind bekannte Verbindungen der organischen Chemie.The acetylene derivatives of the formula (V) and the pivalic acid halides of the formula (VI) are known compounds of organic chemistry.

Die Ketone der Formel (llc) lassen sich herstellen, indem man Ketone der Formeln oder

Figure imgb0013
Figure imgb0014
in welchen R2, X und Y die oben angegebenen Bedeutungen haben,
mit Wasserstoff in Gegenwart eines Verdünnungsmittels, wie beispielsweise Methanol, und in Gegenwart eines Katalysators, wie beispielsweise Raney-Nickel oder Palladium auf Kohle unter Normaldruck oder unter erhöhtem Druck, wie vorzugsweise 30 bis 40 bar, bei Temperaturen zwischen 20 °C und 40 °C selektiv an der Doppelbindung bzw. Dreifachbindung hydriert.The ketones of the formula (IIc) can be prepared by ketones of the formulas or
Figure imgb0013
Figure imgb0014
 in which R 2 , X and Y have the meanings given above,
with hydrogen in the presence of a diluent, such as methanol, and in the presence of a catalyst, such as Raney nickel or palladium on carbon, under normal pressure or under elevated pressure, such as preferably 30 to 40 bar, at temperatures between 20 ° C. and 40 ° C. selectively hydrogenated on the double bond or triple bond.

Bei dem erfindungsgemäßen Verfahren arbeitet man in flüssiger Phase, vorzugsweise in Anwesenheit von Verdünnungsmitteln, unter Verwendung eines suspendierten, pulverförmigen Hydrierungskatalysators. Die Durchführung der erfindungsgemäßen Hydrierung kann diskontinuierlich (chargenweise) oder kontinuierlich als Sumpf- oder Rieselphasenhydrierung in bekannten Hydrierreaktoren, wie Autoklaven, Autoklavenkaskaden, Rohrreaktoren oder Umlaufreaktoren erfolgen. Die bevorzugte Arbeitsweise ist die diskontinuierliche Sumpfphasenhydrierung im Autoklaven bei erhöhtem Druck.The process according to the invention is carried out in the liquid phase, preferably in the presence of diluents, using a suspended, powdery hydrogenation catalyst. The hydrogenation according to the invention can be carried out batchwise or continuously as bottom or trickle-phase hydrogenation in known hydrogenation reactors, such as autoclaves, autoclave cascades, tubular reactors or circulation reactors. The preferred procedure is the discontinuous bottom phase hydrogenation in an autoclave at elevated pressure.

Als Verdünnungsmittel kommen bei der Durchführung des erfindungsgemäßen Verfahrens inerte organische Lösungsmittel in Frage. Hierzu gehören vorzugsweise Alkohole, wie Methanol, Ethanol, Isopropanol oder Ethylenglykol ; Ether, wie Diethylether, Diisopropylether, Ethylenglykolmonomethylether, Ethylenglykoldimethylether, Dioxan oder Tetrahydrofuran ; gesättigte Kohlenwasserstoffe, wie n-Heptan oder Cyclohexan ; sowie Ester, wie Essigsäureethylester.Inert organic solvents are suitable as diluents when carrying out the process according to the invention. These preferably include alcohols, such as methanol, ethanol, isopropanol or ethylene glycol; Ethers such as diethyl ether, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, dioxane or tetrahydrofuran; saturated hydrocarbons such as n-heptane or cyclohexane; as well as esters, such as ethyl acetate.

Für das erfindungsgemäße Verfahren geeignete Hydrierkatalysatoren sind beispielsweise solche, die aus Metallen und/oder Verbindungen von Elementen der achten Nebengruppe des periodischen Systems der Elemente nach Mendelejew bestehen oder diese enthalten. Dabei sind die Metalle Ruthenium, Rhodium, Palladium, Platin, Kobalt und Nickel und deren Verbindungen bevorzugt. Bei den Metallverbindungen kann es sich beispielsweise um Oxide, Hydroxide und/oder Oxihydrate handeln. Zusätzlich können die Metalle Kupfer. Vanadium, Molybdän. Chrom und/oder Mangan, sowie Verbindungen dieser Metalle zugegen sein.Hydrogenation catalysts suitable for the process according to the invention are, for example, those which consist of metals and / or compounds of elements of the eighth subgroup of the periodic system of the elements according to Mendeleev or which contain them. The metals ruthenium, rhodium, palladium, platinum, cobalt and nickel and their compounds are preferred. The metal compounds can be, for example, oxides, hydroxides and / or oxyhydrates. In addition, the metals can be copper. Vanadium, molybdenum. Chromium and / or manganese and compounds of these metals are present.

Die Hydrierkatalysatoren können ausschließlich oder überwiegend aus Wasserstoff-übertragenden Substanzen bestehen, diese können aber auch auf Trägermaterialien aufgebracht sein.The hydrogenation catalysts can consist exclusively or predominantly of hydrogen-transferring substances, but these can also be applied to support materials.

Als Trägermaterialien für die Wasserstoff-übertragenden Substanzen kommen beispielsweise in Frage : anorganische Materialien, wie Kieselgur, Kieselsäure, Aluminium-oxid, Alkali- und Erdalkalisilikate, Aluminiumsilikate, Montmorillonit, Zeolithe, Spinelle, Dolomit, Kaolin, Magnesiumsilikate, Zirkonoxid, Zinkoxid, Calciumcarbonat, Siliciumcarbid, Aluminiumphosphat, Borphosphat, Asbest, Aktivkohle oder Bariumsulfat, aber auch organische Materialien, beispielsweise natürlich vorkommende oder synthetische Verbindungen mit hohen Molekulargewichten wie Seide, Polyamide, Polystyrole, Zellstoff oder Polyurethane. Bevorzugt sind anorganische Trägermaterialien in Pulverform.Possible carrier materials for the hydrogen-transferring substances are, for example: inorganic materials, such as kieselguhr, silica, aluminum oxide, alkali and alkaline earth silicates, aluminum silicates, montmorillonite, zeolites, spinels, dolomite, kaolin, magnesium silicates, zirconium oxide, zinc oxide, calcium carbonate, Silicon carbide, aluminum phosphate, boron phosphate, asbestos, activated carbon or barium sulfate, but also organic materials, for example naturally occurring or synthetic compounds with high molecular weights such as silk, polyamides, polystyrenes, cellulose or polyurethanes. Inorganic carrier materials in powder form are preferred.

Derartige Trägerkatalysatoren können im allgemeinen 0,5 bis 50 Gew.-%, vorzugsweise 1 bis 10 Gew.- % der Wasserstoff-übertragenden Substanz, bezogen auf die Gesamtmasse des Trägerkatalysators, enthalten. Die Wasserstoff-übertragende Substanz kann dabei homogen im Trägermaterial verteilt sein, bevorzugt sind jedoch Katalysatoren, in deren äußerer Schicht oder auf deren Oberfläche die Wasserstoff-übertragende Substanz abgelagert ist. Die Herstellung und die Formgebung der Katalysatoren, die im erfindungsgemäßen Verfahren Verwendung finden können, kann in bekannter Weise erfolgen (siehe beispielsweise Houben-Weyl, Methoden der organischen Chemie, Band IV, Ic, Teil I, S. 16 bis 26, Georg Thieme Verlag, Stuttgart, 1980).Such supported catalysts can generally contain 0.5 to 50% by weight, preferably 1 to 10% by weight, of the hydrogen-transferring substance, based on the total mass of the supported catalyst. The hydrogen-transferring substance can be distributed homogeneously in the support material, but catalysts are preferred, in whose outer layer or on the surface of which the hydrogen-transferring substance is deposited. The preparation and shaping of the catalysts which can be used in the process according to the invention can be carried out in a known manner (see, for example, Houben-Weyl, Methods of Organic Chemistry, Volume IV, Ic, Part I, pp. 16 to 26, Georg Thieme Verlag , Stuttgart, 1980).

Bevorzugte Trägerkatalysatoren sind Ruthenium auf Kohle, Ruthenium auf Aluminiumoxid, Rhodium auf Kohle, Rhodium auf Aluminiumoxid, Palladium auf Kohle, Palladium auf Aluminiumoxid, Palladium auf Calciumcarbonat, Palladium auf Bariumsulfat, Palladium auf Kieselsäure, Platin auf Kohle und Platin auf Aluminiumoxid, Nickel auf Kieselgur, Nickel auf Aluminiumoxid sowie Nickel und Palladium auf Aluminiumoxid.Preferred supported catalysts are ruthenium on carbon, ruthenium on aluminum oxide, rhodium on carbon, rhodium on aluminum oxide, palladium on carbon, palladium on aluminum oxide, palladium on calcium carbonate, palladium on barium sulfate, palladium on silica, platinum on carbon and platinum on aluminum oxide, nickel on diatomaceous earth , Nickel on aluminum oxide and nickel and palladium on aluminum oxide.

Bevorzugte Hydrierkatalysatoren, die ausschließlich oder überwiegend aus Wasserstoff-übertragender Substanz bestehen, sind beispielsweise oxidische Katalysatoren, wie Palladiumoxid, Platinoxid, Rutheniumoxid und/oder Rhodiumoxid/Platinoxid nach Nishimura, ferner durch Reduktion von entsprechenden Metallsalzen oder Metallsalzgemischen mit Alkalihydriden, Alkaliboranaten, Metallalkylen, Hydrazin, Formaldehyd, Wasserstoff oder elektropositiven Metallen herstellbare Schwarzkatalysatoren, wie Palladium/Schwarz, Platin/Schwarz und Rhodium/Schwarz ; sowie Skelettkatalysatoren vom Raney-Typ, wie Raney-Nickel, Raney-Kobalt, Raney-Nickel-Kobalt, Raney-Nickel-Eisen, Raney-Nickel-Kupfer. Raney-Nickel-Eisen-Chrom, Raney-Nickel-Palladium und Raney-Nickel-Eisen-Vanadium.Preferred hydrogenation catalysts which consist exclusively or predominantly of hydrogen-transferring substances are, for example, oxidic catalysts, such as palladium oxide, platinum oxide, ruthenium oxide and / or rhodium oxide / platinum oxide according to Nishimura, furthermore by reduction of corresponding metal salts or metal salt mixtures with alkali metal hydrides, alkali boronates, metal alkyls, hydrazine , Formaldehyde, hydrogen or electropositive metals black catalysts, such as palladium / black, platinum / black and rhodium / black; as well as skeletal catalysts of the Raney type, such as Raney nickel, Raney cobalt, Raney nickel cobalt, Raney nickel iron, Raney nickel copper. Raney nickel iron chromium, Raney nickel palladium and Raney nickel iron vanadium.

Die Auswahl eines oder mehrerer der genannten Hydrierkatalysatoren richtet sich zweckmäßigerweise nach der Konstitution der erfindungsgemäß zu hydrierenden Ausgangsketone der Formeln (lIa), (llb) und. (llc).The selection of one or more of the hydrogenation catalysts mentioned is advantageously based on the constitution of the starting ketones of the formulas (Ia), (IIb) and. (llc).

Enthalten die Ketone der Formeln (lla) und (llb) als Substituent R' gegebenenfalls substituierte Cycloalkenylreste oder gegebenenfalls substituierte Cycloalkylreste, so sind zu deren Überführung in gesättigte Ketone der Formel (I) diejenigen Katalysatoren, die Nickel und/oder Palladium enthalten oder daraus bestehen, besonders bevorzugt.If the ketones of the formulas (IIa) and (IIb) contain, as substituent R ', optionally substituted cycloalkenyl radicals or optionally substituted cycloalkyl radicals, those catalysts which contain or consist of nickel and / or palladium are those which are converted into saturated ketones of the formula (I) , particularly preferred.

Enthalten die Ketone der Formeln (Ila) und (Ilb) als Substituenten R' gegebenenfalls substituierte Arylreste oder handelt es sich um ein Keton der Formel (llc), so sind zu deren Überführung in gesättigte Ketone der Formel (I) diejenigen Katalysatoren, die Ruthenium, Rhodium und/oder Platin enthalten oder daraus bestehen, besonders bevorzugt.If the ketones of the formulas (Ila) and (Ilb) contain substituted or unsubstituted aryl radicals as substituents R 'or if it is a ketone of the formula (IIc), those catalysts which are converted to saturated ketones of the formula (I) are ruthenium , Rhodium and / or platinum contain or consist thereof, particularly preferred.

Die Hydrierkatalysatoren werden im erfindungsgemäßen Verfahren in einer solchen Menge eingesetzt, daß 0,05 bis 2,5, vorzugsweise 0,1 bis 1 Gew.-% Wasserstoff-übertragende Substanz bezogen auf das Gesamtgewicht des Reaktionsgemisches vorliegen.The hydrogenation catalysts are used in the process according to the invention in such an amount that 0.05 to 2.5, preferably 0.1 to 1% by weight of hydrogen-transferring substance, based on the total weight of the reaction mixture, is present.

Zur Durchführung des erfindungsgemäßen Verfahrens können auch Gemische aus zwei oder mehreren der genannten Hydrierkatalysatoren verwendet werden.Mixtures of two or more of the hydrogenation catalysts mentioned can also be used to carry out the process according to the invention.

Die katalytische Aktivität der Hydrierkatalysatoren bleibt bei der Durchführung des erfindungsgemäßen Verfahrens im allgemeinen weitgehend erhalten, so daß diese bei diskontinuierlicher Arbeitsweise wiederholt eingesetzt werden können und bei kontinuierlicher Arbeitsweise längere Zeit in Gebrauch bleiben können.The catalytic activity of the hydrogenation catalysts is generally largely retained when the process according to the invention is carried out, so that they can be used repeatedly in a batch mode and can be used for a long time in a continuous mode.

Die Reaktionstemperaturen können in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man im Bereich zwischen 0 °C und 150 °C, vorzugsweise zwischen 20 °C und 120 °C. Für die Hydrierung von aliphatischen und/oder cycloaliphatischen C-C-Mehrfachbindungen in den Ketonen der Formeln (Ila) und (Ilb) mit den dafür bevorzugten Katalysatoren sind Reaktionstemperaturen im Bereich von 20 °C bis 60 °C besonders bevorzugt, während für die Hydrierung von Arylresten in den Ketonen der Formeln (IIa), (Ilb) und (llc) mit den dafür bevorzugten Katalysatoren Temperaturen im Bereich von 60 °C bis 120°C besonders bevorzugt sind.The reaction temperatures can be varied within a wide range. Generally one works in the range between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C. For the hydrogenation of aliphatic and / or cycloaliphatic CC multiple bonds in the ketones of the formulas (Ila) and (Ilb) with the preferred catalysts, reaction temperatures in the range from 20 ° C. to 60 ° C. are particularly preferred, while for the hydrogenation of aryl radicals In the ketones of the formulas (IIa), (IIb) and (IIc) with the preferred catalysts, temperatures in the range from 60 ° C. to 120 ° C. are particularly preferred.

Die erfindungsgemäßen Hydrierungen werden vorzugsweise bei erhöhtem Druck durchgeführt. Im allgemeinen arbeitet man zwischen 1 und 150 bar, vorzugsweise bei 20 bis 120 bar. Für die Hydrierung von aliphatischen und/oder cycloaliphatischen C-C-Mehrfachbindungen in den Ketonen der Formeln (Ila) und (IIb) mit den dafür bevorzugten Katalysatoren sind Drucke im Bereich von 5 bis 50 bar besonders bevorzugt, während für die Hydrierung von Arylresten in den Ketonen der Formeln (IIa), (Ilb) und (llc) mit den dafür bevorzugten Katalysatoren Drucke im Bereich von 5 bis 120 bar besonders bevorzugt sind.The hydrogenations according to the invention are preferably carried out at elevated pressure. In general, one works between 1 and 150 bar, preferably at 20 to 120 bar. For the hydrogenation of aliphatic and / or cycloaliphatic CC multiple bonds in the ketones of the formulas (Ila) and (IIb) with the preferred catalysts, pressures in the range from 5 to 50 bar are particularly preferred, while for the hydrogenation of aryl radicals in the ketones of the formulas (IIa), (IIb) and (IIc) with the preferred catalysts, pressures in the range from 5 to 120 bar are particularly preferred.

Die für das erfindungsgemäße Verfahren erforderliche Reaktionszeit ist abhängig von der Reaktionstemperatur, dem Wasserstoffpartialdruck, der Intensität der Durchmischung des Reaktionsgemisches und von der Aktivität und Konzentration des Hydrierkatalysators. Im allgemeinen liegt die erforderliche Reaktionszeit im Bereich von 15 Minuten bis zu mehreren Stunden.The reaction time required for the process according to the invention depends on the reaction temperature, the hydrogen partial pressure, the intensity of the mixing of the reaction mixture and on the activity and concentration of the hydrogenation catalyst. In general, the reaction time required ranges from 15 minutes to several hours.

Das erfindungsgemäße Verfahren kann beispielsweise in der einfachsten Ausführungsform diskontinuierlich in folgender Weise durchgeführt werden : Ein mit einer Rühr- oder Mischeinrichtung versehener, temperierbarer Autoklav wird in geeigneter Weise mit einem Keton der Formel (Ila), (Ilb) oder (llc), dem Hydrierungskatalysator und dem Verdünnungsmittel beschickt. Nachdem der Autoklav entlüftet und sodann Wasserstoff bis zu dem gewünschten Druck aufgedrückt worden ist, wird das Gemisch unter intensiver Durchmischung auf die gewählte Reaktionstemperatur erhitzt. Der Reaktionsverlauf läßt sich leicht durch Messung des Wasserstoffverbrauches, der durch weitere Wasserstoffzufuhr ausgeglichen wird, verfolgen. Die Hydrierung ist beendet, wenn kein Wasserstoff mehr verbraucht wird und die verbrauchte Wasserstoffmenge etwa der theoretisch erforderlichen Wasserstoffmenge entspricht.For example, the simplest embodiment of the process according to the invention can be carried out discontinuously in the following manner: A temperature-controlled autoclave provided with a stirring or mixing device is suitably treated with a ketone of the formula (Ila), (Ilb) or (IIc), the hydrogenation catalyst and charged with the diluent. After the autoclave has been vented and hydrogen has been injected to the desired pressure, the mixture is heated to the selected reaction temperature with thorough mixing. The course of the reaction can easily be followed by measuring the hydrogen consumption, which is compensated for by further hydrogen supply. The hydrogenation is complete when no more hydrogen is consumed and the amount of hydrogen consumed corresponds approximately to the amount of hydrogen theoretically required.

Nach beendeter Hydrierung wird das Reaktionsgemisch abgekühlt, entspannt und in bekannter Weise, beispielsweise durch Abfiltrieren des Katalysators und Destillieren des Verdünnungsmittels, aufgearbeitet.After the hydrogenation has ended, the reaction mixture is cooled, let down and worked up in a known manner, for example by filtering off the catalyst and distilling off the diluent.

In einer besonderen Ausführungsform der erfindungsgemäßen Umsetzung wird so verfahren, daß in einer ersten Stufe Ketone der Formel (lla), die als Substituenten R' einen gegebenenfalls substituierten Arylrest tragen, zu entsprechenden Ketonen der Formel (llc) hydriert werden, die dann in einer zweiten Stufe zu den Endprodukten der Formel (I) hydriert werden (vgl. auch die Herstellungsbeispiele). Hervorzuheben ist, daß mit hoher Selektivität nur die C-C-Mehrfachbindungen hydriert werden, während die CO-Doppelbindung erhalten bleibt.In a particular embodiment of the reaction according to the invention, the procedure is such that in a first stage ketones of the formula (IIa) which bear an optionally substituted aryl radical as substituents R 'are hydrogenated to corresponding ketones of the formula (IIc), which are then in a second stage Stage to the end products of formula (I) are hydrogenated (see also the preparation examples). It should be emphasized that only the C-C multiple bonds are hydrogenated with high selectivity, while the CO double bond is retained.

Wie schon erwähnt, stellen die neuen 5-Cycloalkyl-2,2-dimethyl-pentan-3-one der Formel (I) interessante Zwischenprodukte zur Synthese von 4-Azolyl-5-cycloalkyl-2.2-dimethyl-pentan-3-onen und -olen mit fungiziden und pflanzenwuchsregulierenden Eigenschaften dar.As already mentioned, the new 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula (I) represent interesting intermediates for the synthesis of 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and -ols with fungicidal and plant growth regulating properties.

Solche 4-Azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-one und -ole der Formel (VII)

Figure imgb0015
in welcher

  • R, X und Y die oben angegebenen Bedeutungen haben und
  • A für eine Keto- oder die CH(OH)-Gruppe steht.

lassen sich herstellen, indem man 5-Cycloalkyl-2.2-dimethyl-pentan-3-one der Formel (I)
Figure imgb0016
in welcher R, X und Y die oben angegebenen Bedeutungen haben, mit Chlor oder Brom in Gegenwart eines inerten organischen Lösungsmittels, wie beispielsweise Ether, chlorierten oder nicht chlorierten Kohlenwasserstoffen, bei Raumtemperatur umsetzt, oder mit üblichen Chlorierungsmitteln, wie beispielsweise Sulfurylchlorid, bei 20 °C bis 60 °C umsetzt ; anschließend die so erhaltenen Halogenketone der Formel (VIII)
Figure imgb0017
in welcher
  • R, X und Y die oben angegebenen Bedeutungen haben und
  • Z für Chlor oder Brom steht,

mit 1,2,4-Triazol in Gegenwart eines inerten organischen Lösungsmittels, wie beispielsweise Acetonitril, und in Gegenwart eines Säurebindemittels, wie beispielsweise Kaliumcarbonat oder in Gegenwart eines Überschusses an 1,2,4-Triazol, bei Temperaturen zwischen 60 °C und 120 °C umsetzt ;
und gegebenenfalls anschließend die so erhaltenen 4-Azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-one der Formel (Vlla)
Figure imgb0018
in welcher R, X und Y die oben angegebenen Bedeutungen haben,
durch Umsetzung mit komplexen Hydriden, wie Natriumborhydrid oder Lithiumalanat, in Gegenwart eines polaren organischen Lösungsmittels, wie z. B. eines Alkoholes, bei Temperaturen zwischen 0 °C und 30 °C reduziert ; oder durch Umsetzung mit Aluminiumisopropylat in Gegenwart eines Verdünnungsmittels, wie z. B. Isopropanol, bei Temperaturen von 20 °C bis 120 °C reduziert.Such 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and ols of the formula (VII)
Figure imgb0015
 in which
  • R, X and Y have the meanings given above and
  • A represents a keto or the CH (OH) group.

can be prepared by using 5-cycloalkyl-2,2-dimethyl-pentan-3-one of the formula (I)
Figure imgb0016
 in which R, X and Y have the meanings given above, with chlorine or bromine in the presence of an inert organic solvent, such as ether, chlorinated or non-chlorinated hydrocarbons, at room temperature, or with conventional chlorinating agents, such as sulfuryl chloride, at 20 ° C converts to 60 ° C; then the halogen ketones of the formula (VIII) thus obtained
Figure imgb0017
 in which
  • R, X and Y have the meanings given above and
  • Z represents chlorine or bromine,

with 1,2,4-triazole in the presence of an inert organic solvent, such as acetonitrile, and in the presence of an acid binder, such as potassium carbonate or in the presence of an excess of 1,2,4-triazole, at temperatures between 60 ° C and 120 ° C converts;
and optionally then the 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones thus obtained, of the formula (VIIa)
Figure imgb0018
 in which R, X and Y have the meanings given above,
by reaction with complex hydrides, such as sodium borohydride or lithium alanate, in the presence of a polar organic solvent, such as. B. an alcohol, reduced at temperatures between 0 ° C and 30 ° C; or by reaction with aluminum isopropylate in the presence of a diluent, such as. B. isopropanol, reduced at temperatures from 20 ° C to 120 ° C.

Die 4-Azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-one und -ole der Formel (VII) weisen starke fungizide und pflanzenwuchsregulierende Eigenschaften auf (vgl. EP-B 0 031 911 und EP-B 0 032 200).The 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and ols of the formula (VII) have strong fungicidal and plant growth-regulating properties (cf. EP-B 0 031 911 and EP-B 0 032 200).

Die Herstellung und die Verwendung der erfindungsgemäßen Substanzen geht aus den folgenden Beispielen hervor.The preparation and use of the substances according to the invention can be seen from the following examples.

HerstellungsbeispieleManufacturing examples Beispiel 1example 1

Figure imgb0019
Figure imgb0019

Verfahrensvariante 1Process variant 1 1. Stufe :1st stage :

Figure imgb0020
Figure imgb0020

Ein 120 I Rührautoklav aus Edelstahl, der mit Hilfe eines regelbaren Thermostaten temperiert werden kann, wurde mit 30 kg (133,9 Mol) 2,2-Bisfluormethyl-5-phenyl-pent-4-en-3-on, 60 1 Methanol und 0,6 kg Raney-Nickel beschickt.A 120 l stirred autoclave made of stainless steel, which can be tempered with the aid of a controllable thermostat, was mixed with 30 kg (133.9 mol) of 2,2-bisfluoromethyl-5-phenyl-pent-4-en-3-one, 60 l of methanol and 0.6 kg of Raney nickel.

Nach Verschließen des Autoklaven und Verdrängen der Luft mit Stickstoff wurde das eingesetzte Gemisch mit Wasserstoff bis zu einem Druck von 30 bar beaufschlagt und unter Rühren auf 30 °C erhitzt. Sobald diese Temperatur erreicht war, wurde des Wasserstoffdruck auf 40 bar erhöht und nach Maßgabe des Wasserstoff-Verbrauches während der gesamten Reaktionszeit aufrechterhalten.After closing the autoclave and displacing the air with nitrogen, the mixture used was pressurized with hydrogen up to a pressure of 30 bar and heated to 30 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was increased to 40 bar and maintained in accordance with the hydrogen consumption during the entire reaction time.

Nachdem die Wasserstoffaufnahme nach etwa 5 Stunden beendet war, wurde zur Vervollständigung der Umsetzung noch eine Stunde unter den vorangenannten Hydrierbedingungen weiter gerührt, anschließend auf Raumtemperatur abgekühlt und auf Normaldruck entspannt.After the hydrogen uptake had ended after about 5 hours, the reaction was continued for a further hour under the aforementioned hydrogenation conditions, then cooled to room temperature and let down to atmospheric pressure.

Die durch Filtration vom Katalysator abgetrennte Produktlösung wurde ohne Isolierung direkt weiter in der 2. Stufe umgesetzt. Das erhaltene 2,2-Bisfluormethyl-5-phenyl-pentan-3-on hat einen Gehalt von 98 % (gaschromatographisch bestimmt).The product solution separated from the catalyst by filtration was reacted directly in the second stage without isolation. The 2,2-bisfluoromethyl-5-phenyl-pentan-3-one obtained has a content of 98% (determined by gas chromatography).

2. Stufe :2nd stage:

Figure imgb0021
Figure imgb0021

Ein 120 I Rührautoklav aus Edelstahl, der mit Hilfe eines regelbaren Thermostaten temperiert werden kann, wurde mit einer Lösung von 29,7 kg (131,4 Mol) 2,2-Bisfluormethyl-5-phenyl-pentan-3-on in 60 I Methanol und 0,72 kg eines 5 % Ruthenium auf Aktivkohle enthaltenden Katalysators beschickt.A 120 I stirred autoclave made of stainless steel, which can be tempered with the aid of an adjustable thermostat, was mixed with a solution of 29.7 kg (131.4 mol) of 2,2-bisfluoromethyl-5-phenyl-pentan-3-one in 60 I Methanol and 0.72 kg of a catalyst containing 5% ruthenium on activated carbon are charged.

Nach Verschließen des Autoklaven und Verdrängen der Luft mit Stickstoff wurde das eingesetzte Gemisch mit Wasserstoff bis zu einem Druck von 50 bar beaufschlagt und unter Rühren auf 90 °C erhitzt. Sobald diese Temperatur erreicht war, wurde der Wasserstoffdruck auf 100 bar erhöht und nach Maßgabe des Wasserstoff-Verbrauches während der gesamten Reaktionszeit aufrechterhalten.After closing the autoclave and displacing the air with nitrogen, the mixture used was pressurized with hydrogen up to a pressure of 50 bar and heated to 90 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was increased to 100 bar and maintained in accordance with the hydrogen consumption during the entire reaction time.

Nachdem die Wasserstoffaufnahme nach etwa 6 Stunden beendet war, wurde zur Vervollständigung der Umsetzung noch eine Stunde unter den vorangenannten Hydrierbedingungen weiter gerührt, anschließend auf Raumtemperatur abgekühlt und auf Normaldruck entspannt.After the hydrogen uptake had ended after about 6 hours, the reaction was continued for a further hour under the aforementioned hydrogenation conditions, then cooled to room temperature and let down to atmospheric pressure.

Die durch Filtration vom Katalysator abgetrennte Produktlösung wurde im Rotationsverdampfer vom Methanol befreit.The product solution separated from the catalyst by filtration was freed of the methanol in a rotary evaporator.

Man erhielt 30,3 kg (99,4 % der Theorie) 2,2-Bisfluormethyl-5-cyclohexyl-pentan-3-on als Öl mit einem Gehalt von 96 % (gaschromatographisch bestimmt).30.3 kg (99.4% of theory) of 2,2-bisfluoromethyl-5-cyclohexyl-pentan-3-one were obtained as an oil with a content of 96% (determined by gas chromatography).

Herstellung des Ausgangsproduktes :Production of the starting product:

Figure imgb0022
Figure imgb0022

Eine Mischung von 106,1 g (1 Mol) Benzaldehyd, 135,1 g (1 Mol) 3,3-Bisfluormethyl-butan-2-on, 300 g Methanol und 40 g (1 Mol) Natriumhydroxid in 70 g Wasser wurde 3 Stunden bei Raumtemperatur gerührt. Anschließend wurde das kristalline Produkt abfiltriert und getrocknet.A mixture of 106.1 g (1 mole) of benzaldehyde, 135.1 g (1 mole) of 3,3-bisfluoromethyl-butan-2-one, 300 g of methanol and 40 g (1 mole) of sodium hydroxide in 70 g of water became 3 Stirred for hours at room temperature. The crystalline product was then filtered off and dried.

Man erhielt 201,8 g (90 % der Theorie) 2,2-Bisfluormethyl-5-phenyl-pent-4-en-3-on vom Schmelzpunkt 45 °C.201.8 g (90% of theory) of 2,2-bisfluoromethyl-5-phenyl-pent-4-en-3-one with a melting point of 45 ° C. were obtained.

Beispiel 2Example 2

Figure imgb0023
Figure imgb0023

Verfahrensvariante 2Process variant 2

Ein 0.7 I Rührautoklav aus Edelstahl, der mit Hilfe eines regelbaren Thermostaten temperiert werden kann, wurde mit 112 g (0,5 Mol) 2,2-Bisfluormethyl-5-phenyl-pent-4-en-3-on, 300 ml Methanol, 2,8 g eines 5 % Palladium auf Aktivkohle enthaltenden Katalysators und 2,8 g eines 5 % Ruthenium auf Aktivkohle enthaltenden Katalysators beschickt.A 0.7 I stirred autoclave made of stainless steel, which can be tempered with the aid of a controllable thermostat, was mixed with 112 g (0.5 mol) of 2,2-bisfluoromethyl-5-phenyl-pent-4-en-3-one, 300 ml of methanol , 2.8 g of a catalyst containing 5% palladium on activated carbon and 2.8 g of a catalyst containing 5% ruthenium on activated carbon.

Nach Verschließen des Autoklaven und Verdrängen der Luft durch Stickstoff wurde Wasserstoff bis zu einem Druck von 30 bar zugeführt und unter Rühren auf 40 °C aufgeheizt. Sobald diese Temperatur erreicht war, wurde der Wasserstoffdruck auf 50 bar erhöht und in dieser Höhe bis zum Abklingen der Wasserstoffaufnahme aufrechterhalten (H2-Verbrauch etwa 0,5 Mol in 1,5 Stunden). Anschließend wurde die Reaktionslösung auf 70 °C und der Wasserstoffdruck auf 100 bar erhöht und die Hydrierung unter diesen Bedingungen fortgesetzt, indem ständig Wasserstoff nach Maßgabe des am Druckabfall erkennbaren Wasserstoff-Verbrauchs bis zu einem Druck von 100 bar nachgedrückt wurde (Hz-Verbrauch etwä 1.5 Mol in 5 Stunden).After closing the autoclave and displacing the air with nitrogen, hydrogen was fed in up to a pressure of 30 bar and heated to 40 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was raised to 50 bar and maintained at this level until the hydrogen absorption had ceased (H 2 consumption about 0.5 mol in 1.5 hours). The reaction solution was then increased to 70 ° C. and the hydrogen pressure to 100 bar, and the hydrogenation was continued under these conditions by continuously pressing in hydrogen up to a pressure of 100 bar in accordance with the hydrogen consumption which can be recognized by the pressure drop (H z consumption approx 1.5 moles in 5 hours).

Nachdem die Wasserstoffaufnahme beendet war, wurde auf Raumtemperatur abgekühlt und auf Normaldruck entspannt. Die durch Filtration vom Katalysator abgetrennte Produktlösung wurde im Rotationsverdampfer von Methanol befreit.After the hydrogen uptake had ended, the mixture was cooled to room temperature and depressurized to normal pressure. The product solution separated from the catalyst by filtration was freed of methanol in a rotary evaporator.

Man erhielt 113 g (97,4 % der Theorie) 2,2-Bisfluormethyl-5-cyclohexyl-pentan-3-on als Öl mit einem Gehalt von 89 % (gaschromatographisch bestimmt).113 g (97.4% of theory) of 2,2-bisfluoromethyl-5-cyclohexyl-pentan-3-one were obtained as an oil with a content of 89% (determined by gas chromatography).

Beispiel 3Example 3

Figure imgb0024
Figure imgb0024

Verfahrensvariante 3Process variant 3 1. Stufe :1st stage :

Figure imgb0025
Figure imgb0025

Ein 0,3 I Rührautoklav aus Edelstahl, der mit Hilfe eines regelbaren Thermostaten temperiert werden kann, wurde mit 44,4 g (0,2 Mol) 2.2-Bisfluormethyl-5-phenyl-pent-4-in-3-on, 170 ml Methanol und 5 g Raney-Nickel beschickt.A 0.3 l stirred autoclave made of stainless steel, which can be tempered with the aid of an adjustable thermostat, was mixed with 44.4 g (0.2 mol) of 2,2-bisfluoromethyl-5-phenyl-pent-4-in-3-one, 170 ml of methanol and 5 g of Raney nickel are charged.

Nach Verschließen des Autoklaven und Verdrängen der Luft mit Stickstoff wurde das eingesetzte Gemisch mit Wasserstoff bis zu einem Druck von 30 bar beaufschlagt und unter Rühren auf 30 °C erhitzt. Sobald diese Temperatur erreicht war, wurde der Wasserstoffdruck auf 50 bar erhöht und nach Maßgabe des Wasserstoff-Verbrauches während der gesamten Reaktionszeit aufrechterhalten.After closing the autoclave and displacing the air with nitrogen, the mixture used was pressurized with hydrogen up to a pressure of 30 bar and heated to 30 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was increased to 50 bar and maintained in accordance with the hydrogen consumption during the entire reaction time.

Nachdem die Wasserstoffaufnahme nach etwa 2 Stunden beendet war, wurde zur Vervollständigung der Umsetzung noch eine Stunde unter den vorangenannten Hydrierbedingungen weiter gerührt, anschließend auf Raumtemperatur abgekühlt und auf Normaldruck entspannt.After the hydrogen uptake had ended after about 2 hours, the reaction was continued for a further hour under the aforementioned hydrogenation conditions, then cooled to room temperature and let down to atmospheric pressure.

Die durch Filtration vom Katalysator abgetrennte Produktlösung wurde im Rotationsverdampfer vom Methanol befreit.The product solution separated from the catalyst by filtration was freed of the methanol in a rotary evaporator.

Man erhielt 44,5 g (98,5 % der Theorie) 2,2-Bisfluormethyl-5-phenyl-pentan-3-on als Öl einem Gehalt von 96,5 % (gaschromatographisch bestimmt).44.5 g (98.5% of theory) of 2,2-bisfluoromethyl-5-phenyl-pentan-3-one were obtained as an oil with a content of 96.5% (determined by gas chromatography).

2. Stufe :2nd stage:

Figure imgb0026
Figure imgb0026

Die Umsetzung verlaüft entsprechend der 2. Stufe bei Verfahrensvariante 1.The implementation takes place in accordance with the 2nd stage in process variant 1.

Herstellung des AusgangsproduktesManufacture of the starting product

Figure imgb0027
Figure imgb0027

In 30 ml Pyridin legte man unter Stickstoff 10,1 g (0,1 Mol) Triethylamin und 1,43 g (0,01 Mol) Kupfer-(I)-bromid vor. Man fügte 10,2 g (0,1 Mol) Phenylacetylen zu und ließ 30 Minuten nachrühren. Danach versetzte man die Reaktionsmischung tropfenweise mit 15,6 g (0,1 Mol) a,a-Bisfluormethyl-propionsä- urechlorid und hielt die Temperatur dabei auf 60 °C. Man ließ 15 Stunden bei dieser Temperatur rühren, kühlte ab, wusch mit Wasser, trocknete über Natriumsulfat und engte im Vakuum ein. Der Rückstand wurde durch Destillation gereinigt.10.1 g (0.1 mol) of triethylamine and 1.43 g (0.01 mol) of copper (I) bromide were initially introduced into 30 ml of pyridine under nitrogen. 10.2 g (0.1 mol) of phenylacetylene were added and the mixture was stirred for a further 30 minutes. Thereafter, the reaction mixture was added dropwise with 15.6 g (0.1 mol) of a, a-bisfluoromethyl-propionic acid chloride and the temperature was kept at 60.degree. The mixture was stirred at this temperature for 15 hours, cooled, washed with water, dried over sodium sulfate and concentrated in vacuo. The residue was purified by distillation.

Man erhielt 17,3 g (78 % der Theorie) 2,2-Bisfluormethyl-5-phenyl-pent-4-in-3-on vom Siedepunkt 103 °C bis 105 °C/0,2 mbar.17.3 g (78% of theory) of 2,2-bisfluoromethyl-5-phenyl-pent-4-in-3-one were obtained from the boiling point 103 ° C. to 105 ° C./0.2 mbar.

Beispiel 4Example 4

Figure imgb0028
Figure imgb0028

Verfahrensvariante 4Process variant 4

Ein 0,3 I Rührautoklav aus Edelstahl, der mit Hilfe eines regelbaren Thermostaten temperiert werden kann, wurde mit 24 g (0,106 Mol) 2,2-Bisfluormethyl-5-(cyclohexen-1-yl)-pent-4-in-3-on, 120 ml Methanol und 5 g Raney-Nickel beschickt.A 0.3 l stirred autoclave made of stainless steel, which can be tempered with the aid of an adjustable thermostat, was mixed with 24 g (0.106 mol) of 2,2-bisfluoromethyl-5- (cyclohexen-1-yl) pent-4-in-3 -on, 120 ml of methanol and 5 g of Raney nickel are charged.

Nach Verschließen des Autoklaven und Verdrängen der Luft mit Stickstoff wurde das eingesetzte Gemisch mit Wasserstoff bis zu einem Druck von 50 bar beaufschlagt und unter Rühren auf 50 °C erhitzt. Sobald diese Temperatur erreicht war, wurde der Wasserstoffdruck auf 70 bar erhöht und nach Maßgabe des Wasserstoff-Verbrauches während der gesamten Reaktionszeit aufrechterhalten.After closing the autoclave and displacing the air with nitrogen, the mixture used was pressurized with hydrogen up to a pressure of 50 bar and heated to 50 ° C. with stirring. As soon as this temperature was reached, the hydrogen pressure was increased to 70 bar and maintained in accordance with the hydrogen consumption during the entire reaction time.

Nachdem die Wasserstoffaufnahme beendet war, wurde zur Vervollständigung der Umsetzung noch eine Stunde unter den vorangenannten Hydrierbedingungen weiter gerührt, anschließend auf Raumtemperatur abgekühlt und auf Normaldruck entspannt.After the hydrogen uptake had ended, the reaction was continued for a further hour under the aforementioned hydrogenation conditions, then cooled to room temperature and let down to atmospheric pressure.

Die durch Filtration vom Katalysator abgetrennte Produktlösung wurde am Rotationsverdampfer vom Methanol befreit.The product solution separated from the catalyst by filtration was freed from the methanol on a rotary evaporator.

Man erhielt 23,5 g (95,5% der Theorie) 2,2-Bisfluormethyl-5-cyclohexyl-pentan-3-on als Öl mit einem Gehalt von 88,5 % (gaschromatographisch bestimmt).23.5 g (95.5% of theory) of 2,2-bisfluoromethyl-5-cyclohexyl-pentan-3-one were obtained as an oil with a content of 88.5% (determined by gas chromatography).

Herstellung des AusgangsproduktesManufacture of the starting product

Figure imgb0029
Figure imgb0029

In 30 ml Pyridin legte man unter Stickstoff 10,1 g (0,1 Mol) Triethylamin und 1,43 g (0,01 Mol) Kupfer-(I)-bromid vor. Man fügte 10,6 g (0,1 Mol) Cyclohexen-1-yl-acetylen zu und ließ 30 Minuten nachrühren. Danach versetzte man die Reaktionsmischung tropfenweise mit 15,6 g (0,1 Mol) α,α-Bis-fluormethyl- propionsäurechlorid und hielt die Temperatur auf 70 °C. Man ließ 15 Stunden bei dieser Temperatur nachrühren, kühlte ab, wusch mit Wasser, trocknete über Natriumsulfat und engte im Vakuum ein. Der Rückstand wurde durch Destillation gereinigt.10.1 g (0.1 mol) of triethylamine and 1.43 g (0.01 mol) of copper (I) bromide were initially introduced into 30 ml of pyridine under nitrogen. 10.6 g (0.1 mol) of cyclohexen-1-yl-acetylene were added and the mixture was stirred for 30 minutes. Then the reaction mixture was added dropwise with 15.6 g (0.1 mol) of α, α-bis-fluoromethylpropionoyl chloride and the temperature was kept at 70.degree. The mixture was stirred at this temperature for 15 hours, cooled, washed with water, dried over sodium sulfate and concentrated in vacuo. The residue was purified by distillation.

Man erhielt 18,1 g (80% der Theorie) 2,2-Bisfluormethyl-5-(cyclohexen-1-yl)-pent-4-in-3-on vom Siedepunkt 106 °C bis 109°C/0,3 mbar.18.1 g (80% of theory) of 2,2-bisfluoromethyl-5- (cyclohexen-1-yl) pent-4-in-3-one were obtained from the boiling point 106 ° C. to 109 ° C./0.3 mbar.

Herstellung von 4-Azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-onen der Formel (VII)Preparation of 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula (VII) Beispiel 5Example 5

Figure imgb0030
Figure imgb0030

1. Stufe1st stage

Figure imgb0031
Figure imgb0031

232,3 g (1 Mol) 2,2-Bisfluormethyl-5-cyclohexyl-pentan-3-on (Beispiel 1) wurden auf 80 °C erhitzt und innerhalb eine Stunde tropfenweise mit 161,9 g (1,2 Mol) Sulfurylchlorid versetzt. Man ließ 5 Stunden bei 80 °C nachrühren und destillierte anschließend überschüssiges Sulfurylchlorid im Vakuum ab. Nach dem Abkühlen auf 20 °C wurde mit 500 ml Methylisobutylketon versetzt. Die organische Lösung wurde mit Wasser neutral gewaschen, über Magnesiumsulfat getrocknet und im Vakuum eingeengt. Der Rückstand wurde destilliert.232.3 g (1 mol) of 2,2-bisfluoromethyl-5-cyclohexyl-pentan-3-one (Example 1) were heated to 80 ° C. and dropwise with 161.9 g (1.2 mol) of sulfuryl chloride within one hour transferred. The mixture was left to stir at 80 ° C. for 5 hours and then excess sulfuryl chloride was distilled off in vacuo. After cooling to 20 ° C., 500 ml of methyl isobutyl ketone were added. The organic solution was washed neutral with water, dried over magnesium sulfate and concentrated in vacuo. The residue was distilled.

Man erhielt 252 g (90 % der Theorie) 2,2-Bisfluormethyl-5-chlor-5-cyclohexyl-pentan-3-on vom Siedepunkt 118°C bis 120 °C/2.5 mbar.252 g (90% of theory) of 2,2-bisfluoromethyl-5-chloro-5-cyclohexyl-pentan-3-one were obtained from the boiling point 118 ° C. to 120 ° C./2.5 mbar.

2. Stufe2nd stage

Figure imgb0032
266,7 g (1 Mol) 2,2-Bisfluormethyl-4-chlor-5-cyclohexyl-pentan-3-on, 69,1 g (1 Mol) 1,2.4-Triazol und 165,8 g (1,2 Mol) Kaliumcarbonat in 1 000 ml Methylisobutylketon wurden 6 Stunden unter Rückfluß erhitzt. Nach dem Abkühlen wurde mit verdünnter Salzsäure und mit Wasser neutral gewaschen. Die organische Phase wurde über Magnesiumsulfat getrocknet und im Vakuum eingeengt.
Figure imgb0032
 266.7 g (1 mol) of 2,2-bisfluoromethyl-4-chloro-5-cyclohexyl-pentan-3-one, 69.1 g (1 mol) of 1,2,4-triazole and 165.8 g (1.2 Mol) potassium carbonate in 1,000 ml of methyl isobutyl ketone was heated under reflux for 6 hours. After cooling, the mixture was washed with dilute hydrochloric acid and with water until neutral. The organic phase was dried over magnesium sulfate and concentrated in vacuo.

Man erhielt 329 g (88% der Theorie) 2,2-Bisfluormethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3- on vom Brechungsindex nD 20 = 1,4933.This gave 329 g (88% of theory) of 2,2-bisfluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) pentan-3-one with a refractive index n D 20 = 1.4933 .

Beispiel 6Example 6

Figure imgb0033
299 g (1 Mol) 2,2-Bisfluormethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-on (Beispiel 5) wurden in 300 ml Methanol gelöst und bei 0 °C bis 5°C tropfenweise mit einer Lösung von 13,2 g (0,35 Mol) Natriumborhydrid in 150 ml 0,1 normaler wäßriger Natronlauge versetzt. Nach einer Reaktionszeit von 2 Stunden wurde die Reaktionslösung mit verdünnter wäßriger Salzsäure auf einen pH-Wert von 4 bis 5 eingestellt. Nach Zugabe von 500 ml Wasser kristallisierte das Endprodukt aus.
Figure imgb0033
 299 g (1 mol) of 2,2-bisfluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) pentan-3-one (Example 5) were dissolved in 300 ml of methanol and at 0 ° C to 5 ° C dropwise with a solution of 13.2 g (0.35 mol) of sodium borohydride in 150 ml of 0.1 normal aqueous sodium hydroxide solution. After a reaction time of 2 hours, the reaction solution was adjusted to a pH of 4 to 5 with dilute aqueous hydrochloric acid. After adding 500 ml of water, the end product crystallized out.

Nach Trocknung im Vakuum erhielt man 286 g (95 % der Theorie) 2,2-Bisfluormethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-ol vom Schmelzpunkt 103 °C bis 105 °C.After drying in vacuo, 286 g (95% of theory) of 2,2-bisfluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) -pentan-3-ol with a melting point of 103 ° C. were obtained up to 105 ° C.

VergleichsbeispielComparative example Herstellung des (1,2,4-Triazol-1-yl)-Derivates der FormelPreparation of the (1,2,4-triazol-1-yl) derivative of the formula

Figure imgb0034

nach dem bisher bekannten Verfahren.
Figure imgb0034
according to the previously known method.

1. Stufe1st stage

Figure imgb0035
Figure imgb0035

In einem Dreihalskolben mit Rührer, Tropftrichter und Liebigkühler mit gekühlter Vorlage wurden 400 ml Tetraethylenglykol und 46,4 g Kaliumfluorid (0,8 Mol) vorgelegt und auf 170 °C aufgeheizt. Man legte an den Vorstoß des Liebigkühlers ein Wasserstrahlvakuum (Druck ca. 20 bis 30 mbar) an. Dann wurden innerhalb von 45 Minuten 57,6 g (0,2 Mol) 2-Acetyl-2-methyl-propan-1,3-diol-bismethansulfat, gelöst in 100 ml Tetraethylenglykol, zugetropft. Das entstandene 3,3-Bisfluormethyl-butan-2-on wurde während der Reaktion in die gekühlte Vorlage abdestilliert. Nach dem Zutropfen wurde noch 1 Stunden bei 175 °C weiter destilliert. Das aufgefangene Destillat wurde anschließend redestilliert. Man erhielt 14 g (51,5 % der Theorie) 3,3-Bisfluormethylbutan-2-on vom Kp. 43 bis 46 °C/12 mbar.400 ml of tetraethylene glycol and 46.4 g of potassium fluoride (0.8 mol) were placed in a three-necked flask equipped with a stirrer, dropping funnel and Liebig cooler with a cooled receiver and heated to 170.degree. Man applied a water jet vacuum (pressure approx. 20 to 30 mbar) to the advance of the Liebig cooler. Then 57.6 g (0.2 mol) of 2-acetyl-2-methyl-propane-1,3-diol-bismethanesulfate, dissolved in 100 ml of tetraethylene glycol, were added dropwise within 45 minutes. The resulting 3,3-bisfluoromethyl-butan-2-one was distilled off into the cooled receiver during the reaction. After the dropwise addition, distillation was continued at 175 ° C. for 1 hour. The distillate collected was then redistilled. 14 g (51.5% of theory) of 3,3-bisfluoromethylbutan-2-one having a boiling point of 43 to 46 ° C./12 mbar were obtained.

2. Stufe2nd stage

Figure imgb0036
136 g (1 Mol) 3,3-Bisfluormethylbutan-2-on in 700 ml Methylenchlorid wurden tropfenweise so mit 51 ml (1 Mol) Brom versetzt, daß laufend Entfärbung eintrat. Anschließend wurde das Lösungsmittel im Wasserstrahlvakuum abdestilliert. Man erhielt nahezu quantitativ rohes 3,3-Bisfluormethyl-1-brom-butan-2-on als Öl, das direkt weiter umgesetzt werden konnte.
Figure imgb0036
 136 g (1 mol) of 3,3-bisfluoromethylbutan-2-one in 700 ml of methylene chloride were added dropwise with 51 ml (1 mol) of bromine so that decolorization occurred continuously. The solvent was then distilled off in a water jet vacuum. Almost quantitative crude 3,3-bisfluoromethyl-1-bromobutan-2-one was obtained as an oil, which could be directly reacted further.

3. Stufe3rd stage

Figure imgb0037
215 g (1 Mol) rohes 3,3-Bisfluormethyl-1-brom-butan-2-on wurden bei 30 bis 35 °C zu 84 g (1,2 Mol) 1,2,4-Triazol und 165 g (1,2 Mol) gemahlenem Kaliumcarbonat in 1 I Ethanol getropft. Man ließ über Nacht' bei 40 °C nachrühren, filtrierte danach vom Ungelösten ab und engte das Filtrat ein. Der ölige Rückstand wurde mit Methylenchlorid und Wasser extrahiert, über Natriumsulfat getrocknet und eingeengt. Der Rückstand wurde in Methylenchlorid aufgenommen und mit 140 ml etherischer Salzsäure versetzt. Das entstandene kristalline Produkt wurde abgesaugt, mit 1 Methylenchlorid und 1 I gesättigter, wäßriger Natriumhydrogencarbonatlösung ausgerührt, mit 1 Liter Wasser gewaschen, über Natriumsulfat getrocknet und eingeengt. Man erhielt 73,8 g (36,4 % der Theorie) 3,3-Bisfluormethyl-1-(1,2,4-triazol-1-yl)-butan-2-on als Öl, das direkt weiter umgesetzt werden konnte.
Figure imgb0037
 215 g (1 mol) of crude 3,3-bisfluoromethyl-1-bromobutan-2-one were converted to 84 g (1.2 mol) of 1,2,4-triazole and 165 g (1 , 2 mol) of ground potassium carbonate was dropped in 1 liter of ethanol. The mixture was left to stir overnight at 40 ° C., the undissolved solution was then filtered off and the filtrate was concentrated. The oily residue was extracted with methylene chloride and water, dried over sodium sulfate and concentrated. The residue was taken up in methylene chloride and treated with 140 ml of ethereal hydrochloric acid. The resulting crystalline product was filtered off with suction, stirred with 1 methylene chloride and 1 l of saturated aqueous sodium hydrogen carbonate solution, washed with 1 liter of water, dried over sodium sulfate and concentrated. 73.8 g (36.4% of theory) of 3,3-bisfluoromethyl-1- (1,2,4-triazol-1-yl) -butan-2-one were obtained as an oil which could be reacted directly .

4. Stufe4th stage

Figure imgb0038
Figure imgb0038

Eine Lösung von 101,4 g (1,81 Mol) Kaliumhydroxid in 217,2 ml Wasser wurde bei Raumtemperatur unter Rühren in eine Lösung von 369,4 g (1,81 Mol) 2,2-Bis-fluormethyl-4-(1,2,4-triazol-1-yl)-butan-3-on in 2 Litern Dimethylsulfoxid gegeben. In dieses Gemisch wurde 320,5 g (1,81 Mol) Cyclohexylmethylbromid unter Rühren tropfenweise zugegegeben, wobei die Temperatur des Reaktionsgemisches durch Kühlung zwischen 20 und 40 °C gehalten wurde. Das Reaktionsgemisch wurde noch 15 Stunden bei 60 °C gerührt und dann in 2 Liter Wasser gegossen. Man extrahierte das erhaltene Gemisch zweimal mit je 1 Liter Methylenchlorid, wusch die vereinigten organischen Phasen viermal mit je 2 Litern Wasser, trocknete über Natriumsulfat und zog das Lösungsmittel ab. Das vorliegende ölige Produkt wurde in Aceton aufgenommen, und 326 g Naphthalin-1,5-disulfonsäure wurden zu der Lösung hinzugefügt. Der sich dabei bildende Niederschlag wurde abgesaugt und in 2 Litern Methylenchlorid suspendiert. Diese Suspension wurde zweimal mit je 2 Litern gesättigter, wäßriger Natriumhydrogencarbonat-Lösung geschüttelt. Dann wurde die organische Phase mit 2 Litern Wasser gewaschen und nach dem Trocknen über Natriumsulfat unter vermindertem Druck eingeengt. Man erhielt auf diese Weise 297,5 g g (63 % der Theorie) an 2,2-Bis-fluormethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-on in Form eines Öles. nD20 = 1.4837.A solution of 101.4 g (1.81 mol) of potassium hydroxide in 217.2 ml of water was stirred into a solution of 369.4 g (1.81 mol) of 2,2-bis-fluoromethyl-4- ( 1,2,4-triazol-1-yl) -butan-3-one in 2 liters of dimethyl sulfoxide. 320.5 g (1.81 mol) of cyclohexylmethyl bromide was added dropwise to this mixture with stirring, the temperature of the reaction mixture being kept between 20 and 40 ° C. by cooling. The reaction mixture was stirred for a further 15 hours at 60 ° C. and then poured into 2 liters of water. The mixture obtained was extracted twice with 1 liter of methylene chloride, the combined organic phases were washed four times with 2 liters of water, dried over sodium sulfate and the solvent was stripped off. The present oily product was taken up in acetone and 326 g of naphthalene-1,5-disulfonic acid was added to the solution. The precipitate that formed was suction filtered and suspended in 2 liters of methylene chloride. This suspension was shaken twice with 2 liters of saturated, aqueous sodium hydrogen carbonate solution. Then the organic phase was washed with 2 liters of water and, after drying over sodium sulfate, concentrated under reduced pressure. This gave 297.5 gg (63% of theory) of 2,2-bis-fluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) -pentan-3-one in Form of an oil. nD20 = 1.4837.

Claims (8)

1. Substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula
Figure imgb0057
in which
R represents cycloalkyl which has 5 to 7 carbon atoms and is optionally mono- to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms,
X represents fluorine or chlorine and
Y represents hydrogen, fluorine or chlorine.
2. Process for the preparation of substituted 5-cyclo-alkyl-2,2-dimethyl-pentan-3-ones of the formula
Figure imgb0058
in which
R represents cycloalkyl which has 5 to 7 carbon atoms and is optionally mono to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms,
X represents fluorine or chlorine and
Y represents hydrogen, fluorine or chlorine,

characterised in that ketones of the formulae
Figure imgb0059
Figure imgb0060
or
Figure imgb0061
in which
R' represents cycloalkyl with 5 to 7 carbon atoms, cycloalkenyl with 5 to 7 carbon atoms or phenyl, in each case optionally mono- to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms,
R2 represents phenyl which is optionally mono- to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms and
X and Y have the abovementioned meanings,

are reacted selectively with hydrogen in the presence of a hydrogenation catalyst and if appropriate in the presence of a diluent.
3. Process for the preparation of 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and -ols of the formula
Figure imgb0062
in which
R represents cycloalkyl which has 5 to 7 carbon atoms and is optionally mono- to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms,
X represents fluorine or chlorine and
Y represents hydrogen, fluorine or chlorine, and
A represents a keto or a -CH(OH) group,

characterised in that substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula
Figure imgb0063
in which R, X and Y have the abovementioned meanings, are reacted with chlorine or bromine in the presence of an inert organic solvent, or with chlorinating agents, if appropriate in the presence of a diluent, then the halogenoketones thus obtained, of the formula
Figure imgb0064
in which
R, X and Y have the abovementioned meanings and
Z represents chlorine or bromine,

are reacted with 1,2,4-triazole in the presence of an inert organic solvent, and then, if appropriate, the 4- azolyl-5-cycloalkyl-2,2-dimethylpentan-3-ones thus obtained, of the formula
Figure imgb0065
in which R. X and Y have the abovementioned meanings, are reacted either with complex hydrides in the presence of a polar organic solvent or with aluminium isopropylate in the presence of a diluent.
4. Ketone of the formula
Figure imgb0066
in which
R' represents cycloalkyl with 5 to 7 carbon atoms, cycloalkenyl with 5 to 7 carbon atoms or phenyl in each case optionally mono- to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms,
X represents fluorine or chlorine and
Y represents hydrogen, fluorine or chlorine.
5. Process for the preparation of ketones of the formula
Figure imgb0067
in which
R' represents cycloalkyl with 5 to 7 carbon atoms, cycloalkenyl with 5 to 7 carbon atoms or phenyl, in each case optionally mono- to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms,
X represents fluorine or chlorine and
Y represents hydrogen, fluorine or chlorine,

characterised in that butan-2-ones of the formula
Figure imgb0068
in which X and Y have the abovementioned meanings, are reacted with aldehydes of the formula
Figure imgb0069
in which R' has the abovementioned meanings, in the presence of a diluent and in the presence of a base.
6. Ketones of the formula
Figure imgb0070
in which
R2 represents phenyl which is optionally mono- to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms,
X represents fluorine or chlorine and
Y represents hydrogen, fluorine or chlorine.
7. Process for the preparation of ketones of the formula
Figure imgb0071
in which
R2 represents phenyl which is optionally mono- to trisubstituted by identical or different alkyl radicals with 1 to 3 carbon atoms,
X represents fluorine or chlorine and
Y represents hydrogen, fluorine or chlorine,

characterised in that ketones of the formulae
Figure imgb0072
or
Figure imgb0073
 in which R2, X and Y have the abovementioned meanings, are reacted with hydrogen in the presence of a diluent and in the presence of a catalyst.
8. Substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-one of the formula
Figure imgb0074
EP84113928A 1983-12-01 1984-11-17 Substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-one Expired EP0144033B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3343532 1983-12-01
DE19833343532 DE3343532A1 (en) 1983-12-01 1983-12-01 SUBSTITUTED 5-CYCLOALKYL-2,2-DIMETHYL-PENTAN-3-ONE

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EP0144033B1 true EP0144033B1 (en) 1988-01-20

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US3458569A (en) * 1966-11-17 1969-07-29 Mobil Oil Corp Process for producing methylphosphonodichloridothioate
US3702343A (en) * 1969-08-11 1972-11-07 Int Flavors & Fragrances Inc 2-methyl-2-(tertiary alkyl cyclohexyl) pentan-4-ones and processes
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US4347192A (en) * 1979-07-30 1982-08-31 G. D. Searle & Co. Derivatives of α,β-unsaturated ketones
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